JP3630765B2 - Deposited film manufacturing apparatus and manufacturing method thereof - Google Patents

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【００２３】
【表２】

［実施例３］
図３に示す電子写真用感光体の製造装置を用い、高周波電極として図４−（２）に示す構造の電極を用い、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表３に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は２０ＭＨｚとした。電極の全長は４００ｍｍ、外部導体４０１は外径２０ｍｍ、内径１６ｍｍのＳＵＳ３０４製である。内部導体４０２は外径８ｍｍの円柱状であり、各スリット部において図４−（２）に示したような突出部を設けた。突出部はスリット形状よりも各辺６ｍｍ小さく、外部導体表面より外部に２ｍｍ突出している。スリット４０３は外部導体軸方向に５個、周方向には３こ、合計１５個を配置した。スリットの配置位置は図４−（２）中に示した通りであり、ａ，ｃ，ｅ，ｇ，ｉ，ｋ＝２５ｍｍ、ｂ，ｊ＝６０ｍｍ、ｄ，ｈ＝５０ｍｍ、ｆ＝３０ｍｍである。スリット幅（周方向）は１５ｍｍとした。
このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表４に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。
【００２４】
（比較例２）
高周波電極として、直径２０ｍｍ、長さ４００ｍｍのＳＵＳ３０４製棒状電極を用いる以外は実施例３と同様にして、図３に示す電子写真用感光体の製造装置を用い、表２に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は実施例３と同様に２０ＭＨｚとした。作製されたａ−Ｓｉ感光体を実施例２に用いた本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表４に示す。実施例３と比較し、特性は不十分なものであり、特に帯電能・感度むらにおいて大きな差異が認められた。
【００２５】
【表３】

【００２６】
【表４】

［実施例４］
実施例２に用いた電極を改造し、図５に示すようにスリット部に直径１ｍｍの穴を１個／ｃｍ^２の密度で形成したテフロン材を埋め込み、本実施例用の電極とした。図５において（ｂ）は（ａ）におけるＢ−Ｂ’での断面を示したものであり、５０１は外部導体、５０２は内部導体、５０３は外部導体５０１に設けられたスリットであり、テフロン材により埋められている。テフロン材には上述したように、１個／ｃｍ^２の密度で直径１ｍｍのガス噴出口５０６が設けられている。５０４は同軸部、５０５は非同軸部を示している。このような電極を図３に示すａ−Ｓｉ系感光体製造装置に設置し、更に図３中に示されている原料ガス導入管３５１を除去した。代わって図５に示した構造の高周波電極３０２の内部導体と外部導体の間に原料ガスを導入し、スリット部のテフロン材に設けられたガス噴出口（図５中５０６）より成膜空間内に原料ガスを導入した。
このような装置構成により、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表５に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は１０５ＭＨｚとした。電極の全長は４００ｍｍ、外部導体５０１は外径４０ｍｍ、内径３６ｍｍのＳＵＳ３０４製であり、内部導体５０２は外径１０ｍｍの円柱状である。また、スリット５０３は外部導体軸方向に５個、周方向には３こ、合計１５個を配置されている。スリットの配置位置、各スリットの寸法は実施例２と同様とした。このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表６に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。また、本実施例において高周波電極と原料ガス導入管を兼用させたことにより、作製された感光体上の球状突起が減少し、画像欠陥が非常に少ない極めて良好な電子写真画像が得られた。
【００２７】
（比較例３）
図３に示す電子写真用感光体の製造装置を用い、高周波電極として直径４０１ｍｍ、長さ４００ｍｍのＳＵＳ３０４製棒状電極を用いて実施例４と同様に表５に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は実施例４と同様に１０５ＭＨｚとした。
作製されたａ−Ｓｉ感光体を実施例４に用いた本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行った。
評価結果を表６に示す。実施例４と比較し、特性は不十分なものであり、特に帯電能・感度むら、及び感光体上の球状突起に起因する画像欠陥において大きな差異が認められた。
【００２８】
【表５】

【００２９】
【表６】

［実施例５］
図３に示す電子写真用感光体の製造装置を用い、高周波電極として図６に示す構造の電極を用い、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表７に示す条件で電荷輸送層、電荷発生層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は２００ＭＨｚとした。電極の全長は４００ｍｍ、外部導体６０２は外径２０ｍｍ、内径１６ｍｍのＳＵＳ３０４製である。内部導体６０３は外径８ｍｍの円柱状である。高周波電力放射部６０１はＳＵＳ３０４製であり、外径３０ｍｍ、厚さｌｍｍの円筒状である。内部導体６０３から直径２ｍｍの柱状の高周波電力分割路６０４が外部導体６０２に設けられた直径６ｍｍの孔を通じて高周波電力放射部６０１に接続されている。高周波電力分割路６０４は各点において、周方向に１２０度間隔で３本ずつ設けられている。高周波電力分割路６０４は外部導体軸方向に５個配置されており、各部の寸法はａ，ｋ＝１５ｍｍ、ｂ，ｄ，ｆ，ｈ，ｊ＝５０ｍｍ、ｃ，ｅ，ｇ，ｉ＝３０ｍｍである。
このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表８に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが充分に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。
【００３０】
［実施例６］
図３に示す電子写真用感光体の製造装置を用い、実施例５と同様にして、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表７に示す条件で電荷輸送層、電荷発生層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は２００ＭＨｚとした。電極の全長は４００ｍｍ、外部導体６０２は外径２０ｍｍ、内径１６ｍｍのＳＵＳ３０４製である。内部導体６０３は外径８ｍｍの円柱状である。高周波電力放射部６０１はＳＵＳ３０４製であり、外径３０ｍｍ、厚さｌｍｍの円筒状である。内部導体６０３から直径２ｍｍの柱状の高周波電力分割路６０４が外部導体６０２に設けられた直径６ｍｍの孔を通じて高周波電力放射部６０１に接続されている。高周波電力分割路６０４は各点において、周方向に１２０度間隔で３本ずつ設けられている。高周波電力分割路６０４は外部導体軸方向に５個配置されており、各部の寸法はａ，ｃ，ｅ，ｇ，ｉ，ｋ＝２５ｍｍ、ｂ＝５０ｍｍ、ｄ＝４０ｍｍ、ｆ＝３０ｍｍ、ｈ＝６０ｍｍ、ｊ＝７０ｍｍである。スリット幅（周方向）は３０ｍｍとした。
このような条件で作製されたａ―Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表８に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。
【００３１】
（比較例４）
高周波電極として、直径２０ｍｍ、長さ４００ｍｍのＳＵＳ３０４製棒状電極を用いる以外は実施例５と同様にして、図３に示す電子写真用感光体の製造装置を用い、表７に示す条件で電荷輸送層、電荷発生層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は実施例５、６と同様に２００ＭＨｚとした。
作製されたａ−Ｓｉ感光体を実施例５、６に用いた本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表８に示す。実施例５、６と比較し、帯電能・感度むらが大きく、またその他の特性も実施例５、６と比べ不十分なものであった。
【００３２】
【表７】

【００３３】
【表８】

［実施例７］
図３に示す電子写真用感光体の製造装置を用い、高周波電極として実施例６と同様に図６に示す構造の電極を用い、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表９に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は４５０ＭＨｚとした。電極の全長は４００ｍｍ、外部導体６０２は外径３０ｍｍ、内径２６ｍｍのＳＵＳ３０４製である。内部導体６０３は外径１５ｍｍの円柱状である。高周波電力放射部６０１はＳＵＳ３０４製であり、外径４０ｍｍ、厚さｌｍｍの円筒状である。内部導体６０３から直径２ｍｍの柱状の高周波電力分割路６０４が外部導体６０２に設けられた直径８ｍｍの孔を通じて高周波電力放射部６０１に接続されている。高周波電力分割路６０４は各点において、周方向に１２０度間隔で３本ずつ設けられている。高周波電力分割路６０４は外部導体軸方向に５個配置されており、各部の寸法はａ，ｃ，ｅ，ｇ，ｉ，ｋ＝２５ｍｍ、ｂ＝５０ｍｍ、ｄ＝４０ｍｍ、ｆ＝３０ｍｍ、ｈ＝６０ｍｍ、ｊ＝７０ｍｍである。スリット幅（周方向）は３０ｍｍとした。
このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表１０に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ―Ｓｉ系感光体が作製されることが確認された。
【００３４】
（比較例５）
高周波電極として、直径３０ｍｍ、長さ４００ｍｍのＳＵＳ３０４製棒状電極を用いる以外は実施例７と同様にして、図３に示す電子写真用感光体の製造装置を用い、表９に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は実施例７と同様に４５０ＭＨｚとした。
作製されたａ−Ｓｉ感光体を実施例７に用いた本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表１０に示す。実施例７と比較し、特性は不十分なものであり、特に帯電能・感度むらにおいて大きな差異が認められた。
【００３５】
【表９】

【００３６】
【表１０】

［実施例８］
実施例６に用いた電極を外部導体６０２と内部導体６０３の間に原料ガスを流せるように改造し、その電極を図３に示すａ−Ｓｉ系感光体製造装置に設置し、更に図３中に示されている原料ガス導入管３５１を除去した。原料ガスは外部導体６０２と内部導体６０３の間を通り、外部導体６０２に設けられた高周波電力分割路用孔を経、外部導体６０２と高周波電力放射部６０１の間を通過した後、成膜空間ヘ供給される。
このような装置構成により、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表１１に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は２０ＭＨｚとした。このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表１２に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。また、本実施例において高周波電極と原料ガス導入管を兼用させたことにより、作製された感光体上の球状突起が減少し、画像欠陥が非常に少ない極めて良好な電子写真画像が得られた。
【００３７】
（比較例６）
図３に示す電子写真用感光体の製造装置を用い、高周波電極として直径２０ｍｍ、長さ４００ｍｍのＳＵＳ３０４製棒状電極を用いて実施例４と同様に表１１に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は実施例８と同様に２０ＭＨｚとした。
作製されたａ−Ｓｉ感光体を実施例８に用いた本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表１２に示す。実施例８と比較し、特性は不十分なものであり、特に帯電能・感度むら、及び感光体上の球状突起に起因する画像欠陥において大きな差異が認められた。
【００３８】
【表１１】

【００３９】
【表１２】

［実施例９］
実施例６に用いた電極を外部導体６０２と内部導体６０３の間にＨｅガスを流せるように改造し、その電極を図３に示すａ−Ｓｉ系感光体製造装置に設置した。Ｈｅガスは外部導体６０２と内部導体６０３の間を通り、外部導体６０２に設けられた高周波電力分割路用孔を経、外部導体６０２と高周波電力放射部６０１の間を通過した後、成膜空間へ供給される。Ｈｅガスの流量は１０００ｓｃｃｍとした。一方、原料ガスは原料ガス導入管３５１より成膜空間へ供給される。
このような装置構成により、直径１０８ｍｍ、長さ３５８ｍｍの円筒状アルミニウムシリンダー上に、表１３に示す条件で電荷注入阻止層、光導電層、表面層からなる感光体を作製した。ＶＨＦ電源３１２の発振周波数は３００ＭＨｚとした。
このような条件で作製されたａ−Ｓｉ感光体を本テスト用に改造されたキヤノン製の複写機ＮＰ−６０６０に設置し、感光体の特性の評価を行なった。評価項目は「帯電能」、「感度」、「光メモリー」、「帯電能・感度むら」、「総合画像特性」の５項目とし、実施例１と同様の具体的評価法により各項目の評価を行なった。評価結果を表１４に示す。いずれの項目においても良好な結果が得られ、本発明により特性むらが極めて均一に抑えられた状態で特性が非常に優れたａ−Ｓｉ系感光体が作製されることが確認された。
【００４０】
【表１３】

【００４１】
【表１４】

【００４２】
【発明の効果】
本発明は、以上のように、その高周波電力の供給比率を調整することによって高周波電力を成膜空間内に均一に供給することができ、大面積プラズマの均一化の達成によって、装置の大型化、高価格化、プラズマの不安定化を伴うことなく、成膜条件によらず常に大面積における膜質、膜厚の均一な堆積膜を製造することができる。
特に２０〜４５０ＭＨｚのＶＨＦ電力を用いてａ−Ｓｉ系感光体を製造する場合には、帯電能、感度等の電気特性及び光メモリー、画像流れ、画像欠陥等の画像特性共に良好で、帯電能むら、感度むらが極めて軽減された良好なａ−Ｓｉ系感光体を製造することができる。
また、本発明に関わる高周波電力供給用電極と原料ガス導入管を兼用させた場合には、より効果的に画像欠陥の抑制を達成することができる。
【図面の簡単な説明】
【図１】本発明のａ−Ｓｉ系感光体製造装置に用いることができる高周波電力供給用電極の一例を示した図である。
【図２】本発明のａ−Ｓｉ系感光体製造装置に用いることができる高周波電力供給用電極の一例を示した図である。
【図３】本発明に用いることができるａ−Ｓｉ系感光体製造装置の一例を示した概略図である。
【図４】（１）は本発明の実施例１〜２に、また（２）は本発明の実施例３に用いた高周波電力供給用電極の一例を示した図である。
【図５】本発明の実施例４に用いた高周波電力供給用電極の一例を示した図である。
【図６】本発明の実施例５〜９に用いた高周波電力供給用電極の一例を示した図である。
【図７】従来のＲＦ帯の周波数を用いたＲＦプラズマＣＶＤ法による電子写真用光受容部材の製造装置の一例を示した模式的な構成図である。
【図８】従来のＭＷ帯の周波数を用いたＭＷプラズマＣＶＤ法による電子写真用光受容部材の製造装置の一例を示した模式的な構成図である。
【図９】ａ−Ｓｉ系感光体の層構成の一例を示した図である。
【符号の説明】
１０１、４０１、５０１・・・・・・・・・・外部導体
１０２、４０２、５０２・・・・・・・・・・内部導体
１０３、４０３、５０３・・・・・・・・・・スリット
１０４、５０４・・・・・・・・・・同軸部
１０５、５０５・・・・・・・・・・非同軸部
５０６・・・・・・・・・ ガス噴出口
２０１、６０１・・・・・・・・・・高周波電力放射部
２０２、６０２・・・・・・・・・ 外部導体
２０３、６０３・・・・・・・・・・内部導体
２０４、６０４・・・・・・・・・・高周波電力分割路
３０１・・・・・・・・・・反応容器
３０２・・・・・・・・・・ＶＨＦ電極
３０４・・・・・・・・・・排気管
３０５・・・・・・・・・・円筒状基体
３０６・・・・・・・・・・成膜空間
３０７・・・・・・・・・・発熱体
３０８・・・・・・・・・・回転軸
３０９・・・・・・・・・・モータ
３１０・・・・・・・・・・減速ギア
３１１・・・・・・・・・・高周波マッチングボックス
３１２・・・・・・・・・・高周波電源
３５１・・・・・・・・・・原料ガス導入管
７１００・・・・・・・・・堆積装置
７１１１・・・・・・・・・・反応容器
７１１２・・・・・・・・・・円筒状基体
７１１３・・・・・・・・・・支持体加熱用ヒーター
７１１４・・・・・・・・・・原料ガス導入管
７１１５・・・・・・・・・・マッチングボックス
７１１６・・・・・・・・・・原料ガス配管
７１１７・・・・・・・・・・反応容器リークバルブ
７１１８・・・・・・・・・・メイン排気バルブ
７１１９・・・・・・・・・・真空計
７２００・・・・・・・・・・原料ガス供給装置
７２１１〜７２１６・・・・・・・・・・マスフローコントローラー
７２２１〜７２２６・・・・・・・・・・原料ガスボンベ
７２３１〜７２３６・・・・・・・・・・原料ガスボンベバルブ
７２４１〜７２４６・・・・・・・・・・ガス流入バルブ
７２５１〜７２５６・・・・・・・・・・ガス流出バルブ
７２６１〜７２６６・・・・・・・・・・圧力調整器
８０１・・・・・・・・・・反応容器
８０２・・・・・・・・・・誘電体窓
８０３・・・・・・・・・・導波管
８０４・・・・・・・・・・排気管
８０５・・・・・・・・・・円筒状基体
８０６・・・・・・・・・ 成膜空問
８０７・・・・・・・・・・発熱体
８０８・・・・・・・・・・回転軸
８０９・・・・・・・・・・モータ
８１０・・・・・・・・・・減速ギア
８５１・・・・・・・・・・原料ガス導入管
９００・・・・・・・・・・電子写真用感光体
９０１・・・・・・・・・・支持体
９０２・・・・・・・・・・光導電層
９０３・・・・・・・・・・表面層
９０４・・・・・・・・・・電荷注入阻止層
９０５・・・・・・・・・・電荷発生層
９０６・・・・・・・・・・電荷輸送層[0001]
[Industrial application fields]
The present invention relates to an apparatus for manufacturing a deposited film, particularly an electrophotographic amorphous silicon (hereinafter referred to as a-Si) -based photoreceptor using a plasma CVD method, and a manufacturing method thereof.
[0002]
[Prior art]
The photoconductive material forming the electrophotographic photoreceptor has high sensitivity, a high S / N ratio [photocurrent (Ip) / dark current (Id)], and an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be irradiated. In addition, characteristics such as fast photoresponsiveness, a desired dark resistance value, and harmlessness to the human body during use are required.
In particular, in the case of an electrophotographic light-receiving member incorporated in an electrophotographic apparatus used as an office machine in an office, the above-described pollution-free property is an important point. Hydrogenated amorphous silicon (hereinafter referred to as “a-Si: H”) is a photoconductive material exhibiting excellent properties in this respect. For example, Japanese Patent Publication No. 60-35059 discloses light for electrophotography. Application as a receiving member is described.
In the conventional electrophotographic photoreceptor described above, generally, a conductive support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method is applied on the support. Then, a photoconductive layer made of a-Si is formed by a film forming method such as a photo CVD method or a plasma CVD method.
Among these, a plasma CVD method, that is, a method of decomposing a source gas by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is put to practical use.
Japanese Patent Application Laid-Open No. 56-83746 discloses an electrophotography comprising a conductive support and an a-Si (hereinafter referred to as “a-Si: X”) photoconductive layer containing a halogen atom as a constituent element. Photoconductors have been proposed.
In this publication, by containing 1 to 40 atomic% of halogen atoms in a-Si, heat resistance is high, and good electrical and optical characteristics can be obtained as a photoconductive layer of a photoreceptor for electrophotography. It is said.
Japanese Patent Application Laid-Open No. 57-115556 discloses a photoconductive member having a photoconductive layer formed of an a-Si deposited film, such as electrical and optical characteristics such as dark resistance, photosensitivity, and photoresponsiveness. In order to improve usage environment characteristics such as photoconductive characteristics and moisture resistance, and stability over time, silicon atoms and carbon atoms are included on the photoconductive layer formed of an amorphous material based on silicon atoms. A technique for providing a surface barrier layer composed of a non-photoconductive amorphous material is described.
Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique relating to a photoreceptor on which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. Japanese Patent No. 168161 describes a technique using an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements as a surface layer.
On the other hand, JP-A-60-95551 discloses image formation such as charging, exposure, development and transfer while maintaining the temperature near the surface of the photoreceptor at 30 to 40 ° C. in order to improve the image quality of the amorphous silicon photoreceptor. By performing the process, a technique for preventing a reduction in surface resistance due to moisture adsorption on the surface of the photosensitive member and an image flow generated in association therewith is disclosed.
Japanese Patent Application Laid-Open No. 61-283116 describes a microwave plasma CVD method and apparatus suitable for forming an amorphous semiconductor. In Japanese Patent Laid-Open No. 63-149381, a plurality of cylindrical substrates are arranged concentrically, and an amorphous film is formed on the substrate by applying microwave power to a discharge space surrounded by the cylindrical substrate. The forming technique is described.
These techniques have improved the electrical, optical, and photoconductive characteristics and usage environment characteristics of the a-Si photoconductor for electrophotography, and the image quality has been improved accordingly.
[0003]
The manufacturing apparatus and manufacturing method of such an a-Si photoconductor are roughly as follows.
FIG. 7 is a schematic configuration diagram showing an example of an electrophotographic light receiving member manufacturing apparatus by an RF plasma CVD method (hereinafter abbreviated as “RF-PCVD”) using a frequency in the RF band as a power source.
The configuration of the manufacturing apparatus shown in FIG. 7 is as follows.
This apparatus is roughly divided into a deposition apparatus 7100, a source gas supply apparatus 7200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel 7111. A cylindrical support 7112, a support heating heater 7113, a source gas introduction pipe 7114 are installed in a reaction vessel 7111 in the deposition apparatus 7100, and a high-frequency matching box 7115 is further connected.
The source gas supply device 7200 includes cylinders 7221 to 7226 of source gases such as SiH4, GeH4, H2, CH4, B2H6, and PH3, valves 7231 to 7236, 7241 to 7246, 7251 to 7256, and mass flow controllers 7211 to 7216, Each source gas cylinder is connected to a gas introduction pipe 7114 in the reaction vessel 7111 via a valve 7260.
Formation of the deposited film using this apparatus can be performed as follows, for example.
First, the cylindrical support 7112 is installed in the reaction vessel 7111, and the inside of the reaction vessel 7111 is evacuated by an unillustrated exhaust device (for example, a vacuum pump). Subsequently, the temperature of the cylindrical support 7112 is controlled to a predetermined temperature of 200 ° C. to 350 ° C. by the support heating heater 7113.
In order to cause the source gas for forming the deposited film to flow into the reaction vessel 7111, it is confirmed that the gas cylinder valves 7231 to 7237 and the reaction vessel leak valve 7117 are closed, and the inflow valves 7241 to 7246, the outflow valve After confirming that the valves 7251 to 7256 and the auxiliary valve 7260 are opened, first, the main valve 7118 is opened to exhaust the reaction vessel 7111 and the gas pipe 7116.
Next, the reading of the vacuum gauge 7119 is about 5 × 10^-6When the time becomes Torr, the auxiliary valve 7260 and the outflow valves 7251 to 7256 are closed.
Thereafter, each gas is introduced from the gas cylinders 7221 to 7226 by opening the valves 7231 to 7236, and each gas pressure is adjusted to 2 kg / cm by the pressure regulators 7261 to 7266.²Adjust to. Next, the inflow valves 7241 to 7246 are gradually opened to introduce each gas into the mass flow controllers 7211 to 7216.
After the preparation for film formation is completed as described above, each layer is formed according to the following procedure.
When the cylindrical support 7112 reaches a predetermined temperature, necessary ones of the outflow valves 7251 to 7256 and the auxiliary valve 7260 are gradually opened, and a predetermined gas is reacted from the gas cylinders 7221 to 7226 through the gas introduction pipe 7114. Introduce into the container 7111. Next, the mass flow controllers 7211 to 7216 are adjusted so that each source gas has a predetermined flow rate. At that time, the opening of the main valve 7118 is adjusted while looking at the vacuum gauge 7119 so that the pressure in the reaction vessel 7111 becomes a predetermined pressure of 1 Torr or less. When the internal pressure is stabilized, an RF power source (not shown) having a frequency of 13.56 MHz is set to a desired power, and RF power is introduced into the reaction vessel 7111 through the high-frequency matching box 7115 to cause glow discharge. The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film containing a predetermined silicon as a main component is formed on the cylindrical support 7112. After the formation of the desired film thickness, the supply of RF power is stopped, the outflow valve is closed, the gas flow into the reaction vessel is stopped, and the formation of the deposited film is completed.
By repeating the same operation a plurality of times, a desired multilayered light-receiving layer is formed.
Needless to say, all of the outflow valves other than the necessary gas are closed when forming each layer. Also, the piping for each gas in the reaction vessel 7111 and from the outflow valves 7251 to 7256 to the reaction vessel 7111. In order to avoid remaining in the system, the outflow valves 7251 to 7256 are closed, the auxiliary valve 7260 is opened, the main valve 7118 is fully opened, and the system is once evacuated to high vacuum as necessary.
In order to make the film formation uniform, it is also effective to rotate the support 7112 at a predetermined speed by a driving device (not shown) during the layer formation.
Furthermore, it goes without saying that the above-described gas species and valve operations are changed according to the production conditions of each layer.
On the other hand, development of the deposited film forming apparatus shown in FIG. 8 that can form a plurality of photosensitive members at the same time and has extremely high productivity is being actively promoted.
FIG. 8A is a schematic cross-sectional view, and FIG. 8B is a schematic cross-sectional view taken along the cutting line B-B ′ of FIG. An exhaust pipe 804 is integrally formed on the side surface of the reaction vessel 801, and the other end of the exhaust pipe 804 is connected to an exhaust device (not shown). Waveguides 803 are attached to the upper and lower surfaces of the reaction vessel 801, respectively, and the other end of each waveguide 803 is connected to a microwave power source (not shown). A dielectric window 802 is hermetically sealed at the end of each waveguide 803 on the reaction container 801 side.
Six cylindrical substrates 805 on which a deposited film is formed are arranged so as to be parallel to each other so as to surround the central portion of the reaction vessel 801. Each cylindrical substrate 805 is held by a rotating shaft 808 and heated by a heating element 807. When the motor 809 is driven, the rotation shaft 808 rotates via the reduction gear 810, and the cylindrical base body 805 rotates around its central axis in the generatrix direction. There is a space surrounded by the cylindrical substrate 805 and each dielectric window 802 in the reaction vessel 801, and this space becomes a film formation space 806. A source gas introduction pipe 851 is provided in each gap between two adjacent cylindrical base bodies 805. The source gas introduction pipe 351 introduces the source gas into the film formation space 806.
When an electrophotographic photoreceptor is produced using this apparatus, first, the reaction container 801 is filled with 10^-7After exhausting to Torr or less, the cylindrical substrate 805 is heated and held at a desired temperature by the heating element 807.
Then, the source gas is introduced into the reaction vessel 801 through the source gas introduction pipe 851. At the same time, a microwave having a frequency of 500 MHz or more, preferably 2.45 GHz, is made incident into the reaction vessel 801 through the waveguide 803 and the dielectric window 802. As a result, glow discharge occurs in the film formation space 806, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 805.
At this time, the deposited film can be formed over the entire circumference of the cylindrical substrate 805 by rotating the motor 809.
[0004]
[Problems to be solved by the invention]
Although a good a-Si type photoreceptor is formed by the above-described conventional apparatus and method, at present, improvement of characteristics more than ever is demanded for these, and in order to cope with it, There is a need for further technological improvements. Specifically, the image density unevenness is further reduced, and the afterimage phenomenon on an electrophotographic image called an optical memory is reduced.
In the optical memory, the latent image formed at the previous copy is not completely erased by the next copy, and the previous copy image is faintly formed on the next copy image.
In order to improve such electrophotographic image characteristics, further development of a-Si-based photoreceptor manufacturing technology, particularly a-Si film formation technology, is indispensable.
The current issues in realizing this are mainly summarized in the following two.
One is to make the film quality and film thickness uniform when forming a large area, which is indispensable for reducing image density unevenness, and the other is to improve the film quality indispensable for reducing optical memory. Only when these are achieved simultaneously will the characteristics of the photoreceptor be improved.
[0005]
Many improvements and improvements have been made to improve the quality of the a-Si film not only for the photoreceptor but also for various applications, and the technology has been steadily improved every day.
However, the current situation is that these techniques do not always work effectively due to the speciality of the “large area” of the photoreceptor. Therefore, in the field of manufacturing a-Si-based photoreceptors, the technology for uniformizing film quality and film thickness over a large area plays an extremely important role over other a-Si film application fields.
For example, one of the a-Si film forming techniques that has been attracting attention in recent years is a VHF plasma CVD (hereinafter abbreviated as “VHF-PCVD”) method using high-frequency power in the VHF band. Since the VHF-PCVD method has a high film deposition rate and a high-quality a-Si film can be obtained, various product manufacturing methods using the VHF-PCVD method have been actively developed. However, this VHF-PCVD method is difficult to obtain a uniform plasma over a wide range, that is, to obtain a uniform film quality and film thickness over a wide range. It is in a situation where introduction into body manufacturing is difficult to realize. In other words, by achieving this problem, it becomes possible to introduce a new a-Si film production technique represented by VHF-PCVD into the a-Si series photoreceptor production technique, and to improve the characteristics of the a-Si series photoreceptor. A significant improvement can be expected.
Under such circumstances, in the development of a-Si type photoreceptors using the plasma CVD method, an early improvement of the large area plasma homogenization technique is strongly desired. It is difficult to meet the demand.
[0006]
Therefore, the present invention solves the above problems and is indispensable for improving the characteristics of a deposited film manufacturing apparatus and method, particularly an a-Si photoreceptor, capable of forming a large area with a uniform film thickness and film quality. It is an object of the present invention to provide a deposition film manufacturing apparatus and a manufacturing method thereof that can achieve the uniformization of large-area plasma and improve the characteristics thereof.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention has a means for introducing at least a source gas and high-frequency power into a reaction vessel having a film formation space, and a plasma CVD method for forming a deposited film on a substrate in the reaction vessel In the deposited film manufacturing apparatus according to the present invention, the means for introducing the high-frequency power is constituted by a high-frequency power supply electrode for uniformly supplying the high-frequency power into the film formation space by adjusting the supply ratio of the high-frequency power.In order to adjust the supply ratio of the high-frequency power, a slit is formed in the outer conductor of the coaxial structure transmission line composed of the outer conductor and the inner conductor of the high-frequency power supply electrode.
As a means for adjusting the supply ratio of the high frequency power,SaidConfiguration adjusted by slitOther than beforeIt is possible to adopt a configuration that adjusts according to the area of the high-frequency power radiating portion provided on the outer periphery of the outer conductor, the distance between the high-frequency power radiating portion and the outer conductor, and the distance between the high-frequency power dividing path branched from the inner conductor and the outer conductor. it can.
Further, the inner conductor may be configured to protrude partially on the same surface of the outer conductor or outside thereof through a slit provided in the outer conductor.
Further, in the present invention, it is more effective if the raw material gas is introduced between the outer conductor and the inner conductor and supplied into the film forming space from the electrode surface.
[0008]
Furthermore, the method for producing a deposited film of the present invention includes:In the method for producing a deposited film by plasma CVD, which has means for introducing at least a raw material gas and high frequency power into a reaction vessel having a film formation space, and forms a deposited film on a substrate in the reaction vessel, the high frequency power From the high frequency power supply electrode of the means for introducingVHF power with a frequency of 20 MHz to 450 MHz in the film formation spaceTheSupply ratioBy a slit formed in the outer conductor of the coaxial transmission line composed of the outer conductor and the inner conductor of the high-frequency power supply electrodeTo adjustThanIn the film formation spaceAverageSupply to oneLionIt is characterized by manufacturing a laminated film.
[0009]
[Action]
In the present invention, by adjusting the supply ratio of the high-frequency power as described above, the supply to the film forming space is made extremely uniform.
As a method of supplying high-frequency power to the film formation space, for example, when trying to use a rod-shaped electrode without depending on the means of the present invention, the high-frequency power supply density to the film formation space on the high-frequency power supply side and the non-supply side is generally The problem arises in that they differ greatly.
As a means to solve this, it is conceivable to optimize the film deposition conditions such as gas flow rate, pressure, power, etc. In this case, the conditions for uniform power supply density and the conditions for the best film characteristics are not necessarily the same. The problem of not doing will arise.
Another method is to use two rod-shaped electrodes and supply power from opposite directions. In this case, not only two high-frequency power sources are required, but also power is supplied from these two power sources. Depending on the phase difference of the generated high-frequency power, there is a problem that it is difficult to obtain a stable plasma.
The present invention can achieve the uniformization of a large area plasma by the above-described configuration, and thereby, without increasing the size of the apparatus, increasing the cost, and destabilizing the plasma, it always has a large area regardless of the film forming conditions. The film quality and film thickness can be made uniform.
In the present invention, when used in the VHF-PCVD method under a VHF power of a frequency of 20 to 450 MHz, the high-speed deposition of a high quality film, which is a feature of the VHF-PCVD method, is performed with a uniform film thickness and film quality. Can be achieved while maintaining.
[0010]
Hereinafter, the present invention will be described with reference to the drawings.
FIG. 1- (1) shows an example of a high-frequency power supply electrode that can be used in the present invention.
1A is a schematic view thereof, FIG. 1B is a schematic sectional view taken along a cutting line BB ′ in FIG. 1A, and FIG. 1C is a schematic drawing taken along a cutting line AA ′. It is sectional drawing.
In the figure, 101 is an outer conductor, 102 is an inner conductor, 103 is a slit, 104 is an electrode portion in which the slit 103 is not formed (hereinafter this portion is referred to as a coaxial portion in the embodiment), 105 is the slit 103 This is an electrode portion that is formed (hereinafter, this portion is referred to as a non-coaxial portion in the embodiments).
The outer conductor 101 may be formed of a conductive material, the surface of the insulating material may be coated with a conductive material, or the surface of the conductive material may be coated with an insulating material. In this case, the coating portion may be only the inner surface, only the outer surface, or both sides.
The inner conductor 102 may also be formed of a conductive material, the surface of the insulating material may be coated with a conductive material, or the surface of the conductive material may be coated with an insulating material. Further, the shape may be a cylindrical shape or a columnar shape. Although not shown in the drawing, an insulating material may be partially or wholly inserted between the outer conductor 101 and the inner conductor 102. The slit 103 is formed by opening a part of the outer conductor.
The shape is not particularly limited, and may be a rectangle as shown in the drawing, a square, a circle, an ellipse, or the like. In addition, these slits may be long in the axial direction or long in the circumferential direction.
The size of the slit is not particularly limited and may be adjusted as appropriate so that a desired high-frequency power is supplied from the slit to the film formation space. However, if the slit becomes too small, the reflected power increases depending on the film formation conditions. Since electric power cannot be supplied, or discharge may occur between the outer conductor 101 and the inner conductor 102, a slit size suitable for each film forming condition is selected.
The number and arrangement of the slits are adjusted so that the high frequency power supply to the film formation space is made uniform in each apparatus and each condition, and it is not necessary that the slits have the same shape and size.
Further, the inner conductor 102 does not necessarily have to be in the outer conductor 101 in the entire region, and the inner conductor 102 partially protrudes outside the outer conductor 101 through the slit 103 as shown in FIG. It does not matter, and it may protrude partially to the same plane as the outer conductor 101.
The high frequency power supplied from one end of the inner conductor 102 is transmitted in the direction of the electrode tip along the coaxial structure transmission path constituted by the inner conductor 102 and the outer conductor 101.
In the middle, in the non-coaxial part 105 provided with the slit, a part of the high frequency power is supplied from the slit into the film formation space. The ratio of the high frequency power supplied from the slit to the film formation space can be adjusted by the shape and size of the slit, but the optimum value of these dimensions for uniformly supplying the high frequency power to the film formation space is generated plasma However, the dimensions are not uniquely determined, and these dimensions are adjusted according to the film forming conditions to be used.
Further, in the present invention, when a gas is allowed to flow between the outer conductor 101 and the inner conductor 102 of the electrode, the following further effects can be obtained. First, when the gas to be introduced is relatively difficult to cause discharge such as He or H2, it is possible to prevent the occurrence of discharge between the outer conductor 101 and the inner conductor 102 as described above. In addition, under conditions where discharge does not occur between the outer conductor 101 and the inner conductor 102 (film formation conditions, electrode structure), a source gas can be introduced between the outer conductor 101 and the inner conductor 102, thereby This eliminates the need for a tube and reduces image defects caused by film peeling from the gas tube.
[0011]
FIG. 2 shows another configuration example of the high-frequency power supply electrode in the present invention.
2A is a schematic view thereof, FIG. 2B is a schematic sectional view taken along a cutting line BB ′ in FIG. 2A, and FIG. 2C is a schematic drawing taken along a cutting line AA ′. It is sectional drawing.
This is because a plurality of cylindrical substrates are arranged so as to surround a film forming space in a vacuum-tight reaction vessel, and at least a raw material gas and high-frequency power are introduced into the film forming space to cause glow discharge in the film forming space. In the amorphous silicon photoconductor manufacturing apparatus by plasma CVD method for forming a deposited film on the substrate by being generated, the high-frequency power supply electrode is provided in the film formation space, and at least one of the electrodes The unit has two or more power transmission paths, and the high-frequency power is transmitted from the innermost layer of the power transmission path to the outermost layer and supplied from the outermost layer to the film formation space. Even with such a configuration, the same effect as that of the configuration described above can be obtained.
Hereinafter, this will be described with reference to FIG.
In the figure, 201 is a high-frequency power radiating portion that is an external power transmission path, 202 is a coaxial outer conductor, 203 is a coaxial inner conductor that is an internal power transmission path, and 204 is a high-frequency power dividing path. The high-frequency power radiating portion 201 and the coaxial outer conductor 202 may be formed of a conductive material, or a conductive material may be coated on the surface of the insulating material, and an insulating material may be coated on the surface of the conductive material. It may be coated. In this case, the coating portion may be only the inner surface, only the outer surface, or both sides. The coaxial inner conductor 203 and the high-frequency power dividing path 204 may also be formed of a conductive material, or a conductive material may be coated on the surface of the insulating material, or an insulating material may be coated on the surface of the conductive material. You may do it.
Further, the shape may be a cylindrical shape or a columnar shape. The high-frequency power radiating unit 201 is not limited to the cylindrical shape shown in the figure, and may have another shape. Although not shown in the drawing, an insulating material may be inserted partially or entirely between the coaxial outer conductor 202 and the coaxial inner conductor 203.
The high-frequency power supplied from one end of the coaxial inner conductor 203 is transmitted in the direction of the electrode tip along the coaxial structure transmission line constituted by the coaxial inner conductor 203 and the coaxial outer conductor 202. In the middle, a part of the high-frequency power dividing path 204 branched from the coaxial inner conductor 203 is supplied to the high-frequency power radiating section 201 that also serves as an external power transmission path, and is supplied from the high-frequency power radiating section 201 to the film formation space. The ratio of the high frequency power divided into each high frequency power dividing path 204 is determined by the impedance on the high frequency power dividing path 204 side and the impedance on the coaxial inner conductor 203 side at the branch point.
Therefore, the power supply ratio to each high-frequency power radiating section 201 is adjusted by the area of each high-frequency power radiating section 201, the distance from the coaxial outer conductor 202, and the distance between the high-frequency power dividing path 204 and the coaxial outer conductor 202. However, the optimum values of these dimensions for uniformly supplying high-frequency power to the film formation space differ depending on the characteristics of the plasma generated, so they are not uniquely determined, and these dimensions are adjusted according to the film formation conditions used. To do.
Further, in the present invention, when gas is allowed to flow between the coaxial outer conductor 202 and the coaxial inner conductor 203 of the electrode, the following further effects can be obtained. First, when the introduced gas is relatively difficult to generate discharge such as He and H2, an effect of preventing abnormal discharge between the coaxial outer conductor 202 and the coaxial inner conductor 203 can be obtained. In addition, when a source gas is introduced between the coaxial outer conductor 202 and the coaxial inner conductor 203, a gas pipe is not necessary, and image defects caused by film peeling from the gas pipe can be reduced.
[0012]
Formation of the deposited film by the a-Si photoconductor manufacturing apparatus using the above-described invention can be generally performed by the following procedure.
FIG. 3 is a schematic view showing an example of an a-Si photoconductor manufacturing apparatus that can be used in the present invention. In FIG. 3, 301 is a reaction vessel, 302 is a high frequency electrode, 304 is an exhaust pipe integrally formed on the side surface of the reaction vessel 301, 305 is a cylindrical substrate, 306 is a film formation space, 307 is a heating element, 308 is A rotating shaft, 309 is a motor, 310 is a reduction gear, 311 is a high-frequency matching box, 312 is a high-frequency power source, and 351 is a source gas introduction pipe.
The electrode having the structure of FIG. 1 or FIG. 2 that can be used in the present invention as the high-frequency electrode 302 is used.^-7After exhausting to below Torr, the cylindrical substrate 305 is heated and held at a desired temperature by the heating element 307.
Then, the source gas is introduced into the reaction vessel 301 through the source gas introduction pipe 351. After confirming that the flow rate of the source gas is the set flow rate and that the pressure in the reaction vessel 301 is stable, high frequency power is supplied from the high frequency power supply 312 to the high frequency electrode 302 via the rematching box 311. The high frequency power radiated from the high frequency electrode 302 to the film forming space 306 causes glow discharge in the film forming space 306, and the source gas is excited and dissociated to form a deposited film on the cylindrical substrate 305.
At this time, the deposited film can be formed over the entire circumference of the cylindrical substrate 305 by rotating the motor 309.
[0013]
The layer structure of the a-Si type photosensitive member that can be produced using the present invention is, for example, as follows.
FIG. 9 is a schematic configuration diagram for explaining a layer configuration.
The electrophotographic photoreceptor 900 shown in FIG. 9A is provided with a photoconductive layer 902 made of a-Si: H, X and having photoconductivity on a support 901.
An electrophotographic photoreceptor 900 shown in FIG. 9B includes a photoconductive layer 902 made of a-Si: H, X and having photoconductivity, and an amorphous silicon surface layer 903 on a support 901. It is configured.
An electrophotographic photoreceptor 900 shown in FIG. 9C has a photoconductive layer 902 made of a-Si: H, X and having photoconductivity on a support 901, an amorphous silicon surface layer 903, And an amorphous silicon based charge injection blocking layer 904.
An electrophotographic photoreceptor 900 shown in FIG. 9D is provided with a photoconductive layer 902 on a support 901. The photoconductive layer 902 includes a charge generation layer 905 made of a-Si: H, X and a charge transport layer 906, on which an amorphous silicon-based surface layer 903 is provided.
[0014]
The support for the photoreceptor in the present invention may be conductive or electrically insulating.
Examples of the conductive support include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also, the surface on the side of forming at least the light receiving layer of an electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, or other synthetic resin film or sheet, glass, ceramic, etc. It is also possible to use a support obtained by conducting a conductive treatment.
The shape of the support 901 can be a cylindrical or plate-like endless belt with a smooth surface or an uneven surface, and the thickness thereof is determined as appropriate so that the electrophotographic photoreceptor 900 can be formed as desired. When flexibility as the electrophotographic photoreceptor 900 is required, the electrophotographic photoreceptor 900 can be made as thin as possible within a range in which the function as the support 901 can be sufficiently exhibited. However, the support 901 is usually 10 μm or more from the viewpoint of manufacturing and handling, such as mechanical strength.
[0015]
Next, the photoconductive layer of the photoreceptor produced according to the present invention will be described. The photoconductive layer 902 is formed on the support 901 by appropriately setting numerical conditions of film formation parameters so that desired characteristics can be obtained. In order to form the photoconductive layer 902, basically, a Si supply source gas capable of supplying silicon atoms (Si), a H supply source gas capable of supplying hydrogen atoms (H), and / or a halogen. A source gas for supplying X, which can supply atoms (X), is introduced in a desired gas state into a reaction vessel in which the inside can be depressurized to cause glow discharge in the reaction vessel. A layer made of a-Si: H, X is formed on a predetermined support 901 provided.
In addition, it is necessary for the photoconductive layer 902 to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves layer quality, particularly photoconductivity and charge retention. This is because it is essential for improving the characteristics. Therefore, the content of hydrogen atoms or halogen atoms, or the total amount of hydrogen atoms and halogen atoms is 10 to 40 atom%, more preferably 15 to 25 atom%, based on the sum of silicon atoms and hydrogen atoms or / and halogen atoms. It is desirable that
Examples of substances that can serve as a gas for supplying Si include those in which a gas state such as SiH4, Si2H6, Si3H8, Si4H10, or silicon hydride (silanes) that can be gasified is effectively used. SiH4 and Si2H6 are preferable because they are easy to handle and have good Si supply efficiency.
Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 902 to further facilitate the control of the hydrogen atom introduction ratio, and these gases are further added to obtain good film characteristics. It is also effective to form a layer by mixing a desired amount of H2 and / or He or a silicon compound gas containing hydrogen atoms. In addition, each gas may be mixed in a plurality of types at a predetermined mixing ratio as well as a single type.
Further, as the raw material gas for supplying the halogen atoms, gaseous compounds that can be gasified or gasified such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen are preferably exemplified. Further, a silicon hydride compound containing a halogen atom that is gaseous or can be gasified containing silicon atoms and halogen atoms as constituent elements can also be mentioned as effective. Specific examples of halogen compounds that can be preferably used include interhalogen compounds such as fluorine gas (F2), BrF, ClF, ClF3, BrF3, BrF5, IF3, and IF7. Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon fluorides such as SiF4 and Si2F6.
In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 902, for example, the temperature of the support 901, the reaction of the raw material used to contain the hydrogen atoms or / and halogen atoms What is necessary is just to control the quantity introduce | transduced in a container, discharge electric power, etc.
The photoconductive layer 902 preferably contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the photoconductive layer 902 in a uniformly distributed state, or there may be a portion containing the non-uniformly distributed state in the layer thickness direction. Also good.
Examples of the atoms controlling the conductivity include so-called impurities in the semiconductor field, and atoms belonging to Group IIIb of the periodic table giving p-type conductivity characteristics (hereinafter abbreviated as “Group IIIb atoms”) or An atom belonging to Group Vb of the periodic table giving n-type conduction characteristics (hereinafter abbreviated as “Group Vb atom”) can be used. Specific examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. . Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and P and As are particularly preferable.
The content of atoms controlling the conductivity contained in the photoconductive layer 902 is preferably 1 × 10^-2~ 1x10⁴Atomic ppm, more preferably 5 × 10^-2~ 5x10³Atomic ppm, optimally 1 × 10^-1~ 1x10³The atomic ppm is desirable. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group for introducing a group Vb atom during the layer formation. The source material may be introduced into the reaction vessel in a gas state together with another gas for forming the photoconductive layer 902. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a material that is gaseous at normal temperature and pressure or that can be easily gasified at least under layer formation conditions is adopted. Is desirable.
Specifically, as a raw material material for introducing the Group IIIb atom, for boron atom introduction, boron hydrides such as B2H6, B4H10, B5H9, B5Hll, B6H10, B6Hl2, B6Hl4, BF3, BCl, etc.₃And boron halides such as BBr3. In addition, AlCl₃, GaCl₃, Ga (CH3) 3, InCl₃, TlCl₃Etc. can also be mentioned.
As a raw material for introducing a group Vb atom, phosphorus hydrides such as PH3 and P2H4, PH4I, PF3, PF5, and PCl can be effectively used for introducing a phosphorus atom.₃, PCl₃, Phosphorus halides such as PBr3, PBr5, and PI3. In addition, AsH3, AsF3, AsCl₃, AsBr3, AsF5, SbH3, SbF3, SbF5, SbCl₃, SbCl₃, BiH3, BiCl₃BiBr3 and the like can also be mentioned as effective starting materials for introducing the Group Vb atom.
In addition, the material material for introducing atoms for controlling the conductivity may be diluted with H2 and / or He as necessary.
It is also effective to make the photoconductive layer 903 contain carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atoms and / or oxygen atoms and / or nitrogen atoms is preferably 1 × 10 with respect to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms.^-5-10 atomic%, more preferably 1 × 10^-4~ 8 atomic%, optimally 1 x 10^-3˜5 atomic% is desirable. Carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the photoconductive layer, or non-uniform distribution in which the content varies in the thickness direction of the photoconductive layer. There may be a part with
The layer thickness of the photoconductive layer 902 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 1 to 100 μm, more preferably 20 to 50 μm, and most preferably 23 to It is desirable to be 45 μm.
In order to form the photoconductive layer 902 having desired film characteristics, it is necessary to appropriately set the mixing ratio between the Si supply gas and the dilution gas, the gas pressure in the reaction vessel, the discharge power, and the support temperature. is there.
The optimum flow rate of H2 and / or He used as the dilution gas is selected as appropriate according to the layer design. Similarly, the optimum gas pressure in the reaction vessel is appropriately selected according to the layer design.^-4-10 Torr, preferably 5x10^-4~ 5 Torr, optimally 1x10^-3It is preferable to set to ~ 1Torr.
Although the above-mentioned ranges can be mentioned as the preferable numerical ranges of the support temperature and gas pressure for forming the photoconductive layer, the conditions are not usually determined independently, but the light-receiving member having desired characteristics. It is desirable to determine an optimum value based on mutual and organic relations to form
[0016]
Next, the surface layer of the photoreceptor manufactured according to the present invention will be described.
It is preferable to further form an amorphous silicon-based surface layer 903 on the photoconductive layer 902 formed on the support 901 as described above. The surface layer 903 is provided mainly for the purpose of improving moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.
The surface layer 903 can be made of any material as long as it is an amorphous silicon-based material. For example, the surface layer 903 contains hydrogen atoms (H) and / or halogen atoms (X), and further contains amorphous silicon containing carbon atoms ( Hereinafter referred to as “a-SiC: H, X”), an amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) and further containing oxygen atoms (hereinafter referred to as “a-SiO: H, X”). ), An amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-SiN: H, X”), a hydrogen atom ( H) and / or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as “a-SiCON: H, X”) Materials notation is) such as is preferably used.
The surface layer 903 is prepared by appropriately setting the numerical conditions of the film formation parameters so as to obtain desired characteristics by a vacuum deposited film forming method.
For example, in order to form the surface layer 903 made of a-SiC: H, X, basically, a Si supply source gas that can supply silicon atoms (Si) and carbon atoms (C) can be supplied. A reaction vessel capable of reducing the pressure inside the source gas for supplying C and the source gas for supplying H that can supply hydrogen atoms (H) and / or the source gas for supplying X that can supply halogen atoms (X) From a-SiC: H, X on a support 901 on which a photoconductive layer 902 previously formed at a predetermined position is formed. The layer to be formed may be formed.
The material of the surface layer may be any amorphous material containing silicon, but a compound with a silicon atom containing at least one element selected from carbon, nitrogen, and oxygen is preferable, and in particular, a-SiC is a main component. Is preferred.
The amount of carbon when the surface layer is composed mainly of a-SiC is preferably in the range of 30% to 90% with respect to the sum of silicon atoms and carbon atoms.
In addition, it is necessary that the surface layer 903 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves layer quality, particularly photoconductive properties and charge retention. It is important to improve the characteristics. The hydrogen content is usually 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic% with respect to the total amount of constituent atoms. The fluorine atom content is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%, and most preferably 0.6 to 4 atomic%.
As a substance that can serve as a silicon (Si) supply gas used in the formation of the surface layer, silicon hydrides (silanes) that are in a gas state or can be gasified such as SiH4, Si2H6, Si3H8, Si4H10 are effectively used. Further, SiH4 and Si2H6 are preferable in terms of easy handling at the time of layer formation, good Si supply efficiency, and the like. These source gases for supplying Si may be diluted with a gas such as H2, He, Ar, Ne or the like as necessary.
Examples of substances that can serve as a carbon supply gas include those in which gaseous hydrocarbons such as CH4, C2H6, C3H8, and C4H10, or hydrocarbons that can be gasified are effectively used. CH4 and C2H6 are preferred as the preferable supply efficiency. Further, these source gases for supplying C may be diluted with a gas such as H2, He, Ar, Ne or the like as necessary.
Examples of substances that can serve as a nitrogen or oxygen supply gas include those in which a gas state compound such as NH 3, NO, N 2 O, NO 2, O 2, CO, CO 2, N 2, or the like that can be gasified is effectively used. Further, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H2, He, Ar, Ne or the like as necessary.
Further, in order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 903 to be formed, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms is added to these gases. It is preferable to form a layer by mixing. In addition, each gas may be mixed in a plurality of types at a predetermined mixing ratio as well as a single type.
Preferable examples of the source gas for supplying the halogen atom include gaseous or gasatable halogen compounds such as halogen gas, halides, interhalogen compounds containing halogen, and silane derivatives substituted with halogen. Further, a silicon hydride compound containing a halogen atom that is gaseous or can be gasified containing silicon atoms and halogen atoms as constituent elements can also be mentioned as effective. Specific examples of the halogen compound that can be suitably used in the present invention include interhalogen compounds such as fluorine gas (F2), BrF, ClF, ClF3, BrF3, BrF5, IF3, and IF7. Specific examples of silicon compounds containing halogen atoms, so-called silane derivatives substituted with halogen atoms, include silicon fluorides such as SiF4 and Si2F6.
In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 903, for example, the temperature of the support 901, the reaction vessel of the raw material used to contain hydrogen atoms or / and halogen atoms What is necessary is just to control the quantity introduce | transduced in, discharge electric power, etc.
Carbon atoms and / or oxygen atoms and / or nitrogen atoms may be uniformly contained in the surface layer, or may have a non-uniform distribution in which the content varies in the layer thickness direction of the surface layer. There may be parts.
Further, the surface layer 903 preferably contains atoms for controlling conductivity as required. The atoms that control conductivity may be contained in the surface layer 903 in a uniformly distributed state, or even if there are portions that are contained in a non-uniformly distributed state in the layer thickness direction. Good.
Examples of the atoms controlling the conductivity include so-called impurities in the semiconductor field, and atoms belonging to Group IIIb of the periodic table giving p-type conductivity characteristics (hereinafter abbreviated as “Group IIIb atoms”). Alternatively, an atom belonging to Group Vb of the periodic table giving n-type conduction characteristics (hereinafter abbreviated as “Group Vb atom”) can be used. Specific examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. . Specific examples of the Group Vb atom include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi), and P and As are particularly preferable.
The content of atoms for controlling the conductivity contained in the surface layer 903 is preferably 1 × 10.^-3~ 1x10³Atomic ppm, more preferably 1 × 10^-2~ 5x10²Atomic ppm, optimally 1 × 10^-1~ 1x10²The atomic ppm is desirable. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group for introducing a group Vb atom during the layer formation. The source material may be introduced into the reaction vessel in a gas state together with another gas for forming the surface layer 903. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a material that is gaseous at normal temperature and pressure or that can be easily gasified at least under layer formation conditions is adopted. Is desirable. Specifically, as a raw material material for introducing the Group IIIb atom, boron hydride such as B2H6, B4H10, B5H9, B5H11, B6H10, B6H12, and B6H14 can be used for introducing boron atoms, BF3, BCl.₃And boron halides such as BBr3. In addition, AlCl₃, GaCl₃, Ga (CH3) 3, InCl₃, TlCl₃Etc. can also be mentioned.
As the source material for introducing the Vb group atom, it is effective to use phosphorus hydride such as PH3 and P2H4, PH4I, PF3, PF5, and PCl for introducing the phosphorus atom.₃, PCl₅, Phosphorus halides such as PBr3, PBr5, and PI3. In addition, AsH3, AsF3, AsCl₃, AsBr3, AsF5, SbH3, SbF3, SbF5, SbCl₃, SbCl₅, BiH3, BiCl₃BiBr3 and the like can also be mentioned as effective starting materials for introducing the Group Vb atom.
Further, the starting material for introducing an atom for controlling the conductivity may be diluted with a gas such as H2, He, Ar, Ne or the like if necessary.
The layer thickness of the surface layer 903 is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the light receiving member, and if it exceeds 3 μm, electrophotographic characteristics such as an increase in residual potential are observed.
The surface layer 904 is carefully formed so that its required properties are provided as desired. That is, a substance having Si, C and / or N and / or O, H and / or X as a constituent element takes a form from a crystal to an amorphous structure depending on the formation conditions, and is electrically conductive in terms of electrical properties. In the present invention, a compound having a desired characteristic according to the purpose is exhibited, and a property between a photoconductive property and a non-photoconductive property is exhibited. The formation conditions are strictly selected as desired.
For example, in order to provide the surface layer 903 mainly for the purpose of improving the pressure resistance, the surface layer 903 is formed as a non-single crystal material having a remarkable electrical insulating behavior in a use environment.
In addition, when the surface layer 903 is provided mainly for the purpose of improving the continuous repeated use characteristics and the use environment characteristics, the degree of electrical insulation is relaxed to some extent, and a certain degree of sensitivity to the irradiated light. It is formed as a non-single crystalline material.
In order to form the surface layer 903 having characteristics that can achieve the object, it is necessary to appropriately set the temperature of the support 901 and the gas pressure in the reaction vessel as desired.
The optimum range of the temperature (Ts) of the support 901 is appropriately selected according to the layer design. In a normal case, the temperature is preferably 200 to 350 ° C, more preferably 230 to 330 ° C, and most preferably 250 to 300 ° C. It is desirable to do.
Similarly, the optimum gas pressure in the reaction vessel is appropriately selected according to the layer design. In normal cases, it is preferably 1 × 10.^-4To 10 Torr, more preferably 5 × 10^-4~ 5 Torr, optimally 1x10^-3It is preferable to set to ~ 1Torr.
Although the above-mentioned ranges are mentioned as the preferable numerical ranges of the support temperature and gas pressure for forming the surface layer, the conditions are not usually determined separately, but a light-receiving member having desired characteristics is selected. It is desirable to determine an optimum value based on mutual and organic relations to be formed.
Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms continuously decreases toward the photoconductive layer 902 may be provided between the surface layer 903 and the photoconductive layer 902. This improves the adhesion between the surface layer and the photoconductive layer, reduces the effects of interference due to light reflection at the interface, and at the same time, prevents carrier trapping at the interface and improves the photoreceptor characteristics. Can reach.
[0017]
Next, the charge injection blocking layer of the photoreceptor manufactured according to the present invention will be described.
If necessary, a charge injection blocking layer having a function of blocking charge injection from the conductive support side may be provided between the conductive support and the photoconductive layer. That is, the charge injection blocking layer has a function of blocking charge injection from the support side to the photoconductive layer side when the surface of the photoconductor is subjected to charging treatment with a constant polarity, When subjected to the treatment, such a function is not exhibited, and it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer.
The atoms controlling the conductivity contained in the layer may be uniformly distributed in the layer, or evenly distributed in the layer thickness direction, but unevenly distributed. There may be a portion that is contained in the state. When the distribution concentration is not uniform, it is preferable to contain it so as to be distributed in a large amount on the support side.
However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to uniformly contain it in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction.
Examples of the atoms controlling the conductivity contained in the charge injection blocking layer include so-called impurities in the semiconductor field, and atoms belonging to Group IIIb of the periodic table giving p-type conduction characteristics (hereinafter referred to as “Group IIIb”). Atoms ”(abbreviated as“ atoms ”) or atoms belonging to group Vb of the periodic table giving n-type conduction properties (hereinafter abbreviated as“ group Vb atoms ”) can be used.
Specific examples of the group IIIb atom include B (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and B, Al, and Ga are particularly preferable. is there. Specific examples of the group Vb atom include P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), and P and As are particularly preferable.
The content of atoms for controlling the conductivity contained in the charge injection blocking layer is appropriately determined as desired, but is preferably 10 to 1 × 10.⁴Atomic ppm, more preferably 50-5 × 10³Atomic ppm, optimally 1 × 10²~ 1x10³The atomic ppm is desirable.
Further, the charge injection blocking layer contains at least one of carbon atom, nitrogen atom and oxygen atom, thereby improving the adhesion between the charge injection blocking layer and another layer provided in direct contact with the charge injection blocking layer. More can be achieved.
The carbon atoms, nitrogen atoms, or oxygen atoms contained in the layer may be uniformly distributed in the layer, or may be uniformly contained in the layer thickness direction, but nonuniformly. There may be a portion contained in a distributed state. However, in any case, in the in-plane direction parallel to the surface of the support, it is necessary to uniformly contain it in a uniform distribution from the viewpoint of achieving uniform characteristics in the in-plane direction.
The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire layer region of the charge injection blocking layer is appropriately determined so that the object of the present invention can be effectively achieved. In the case of 2 or more types, the total amount is preferably 1 × 10^-3~ 50 atomic%, more preferably 5 x 10^-3~ 30 atomic%, optimally 1 x 10^-2Desirably, it is set to -10 atomic%.
In addition, hydrogen atoms and / or halogen atoms contained in the charge injection blocking layer compensate for dangling bonds existing in the layer, and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms in the charge injection blocking layer is preferably 1 to 50 atom%, more preferably 5 to 40 atom%, and most preferably 10 to 30 atoms. % Is desirable.
The layer thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, and most preferably from 0.5 to 0.5 in view of obtaining desired electrophotographic characteristics and economic effects. It is desirable to be 3 μm.
In order to form the charge injection blocking layer, a vacuum deposition method similar to the method for forming the photoconductive layer described above is employed. Similar to the photoconductive layer 902, it is necessary to appropriately set the mixing ratio between the Si supply gas and the dilution gas, the gas pressure in the reaction vessel, the discharge power, and the temperature of the support 901.
The optimum flow rate of the dilution gas H2 and / or He is appropriately selected according to the layer design, but H2 and / or He is usually 1 to 20 times that of the Si supply gas, preferably 3 times. It is desirable to control within a range of ˜15 times, optimally 5˜10 times.
Similarly, the optimum gas pressure in the reaction vessel is appropriately selected according to the layer design.^-4-10 Torr, preferably 5x10^-4~ 5 Torr, optimally 1x10^-3It is preferable to set to ~ 1Torr.
Although the above-mentioned ranges are mentioned as desirable numerical ranges of the mixing ratio of the dilution gas, the gas pressure, the discharge power, and the support temperature for forming the charge injection blocking layer, these layer formation factors are usually independently and separately. Rather than being determined, it is desirable to determine the optimum value of each layer creation factor based on mutual and organic relevance in order to form a surface layer having desired properties.
For the purpose of further improving the adhesion between the support 901 and the photoconductive layer 902 or the charge injection blocking layer 904, for example, Si 3 N 4, SiO 2, SiO, or silicon atoms are used as a base, and hydrogen atoms and / or halogens are used. An adhesion layer made of an amorphous material containing atoms and carbon atoms and / or oxygen atoms and / or nitrogen atoms may be provided. Furthermore, you may provide the light absorption layer for preventing generation | occurrence | production of the interference pattern by the reflected light from a support body.
[0018]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0019]
[Example 1]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, an electrode having the structure shown in FIG. 4- (1) is used as a high-frequency electrode, and a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm is shown in Table 1. A photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was produced under the conditions. The oscillation frequency of the VHF power supply 312 was 450 MHz. The overall length of the electrode is 400 mm, and the outer conductor 101 is made of SUS304 having an outer diameter of 40 mm and an inner diameter of 36 mm. The inner conductor 102 has a cylindrical shape with an outer diameter of 10 mm. In addition, five slits 103 in the axial direction of the outer conductor and three in the circumferential direction are arranged in total. The arrangement positions of the slits are as shown in FIG. 4- (1), where a, k = 15 mm, b, d, f, h, j = 50 mm, c, e, g, i = 30 mm. The slit width (circumferential direction) was 30 mm.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. Evaluation items were five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”, and each item was evaluated by the following specific evaluation method.
“Chargeability”: Measures the dark portion potential at the position of the developing device when a constant current is passed through the main charger of the copying machine. Therefore, the larger the dark part potential, the better the charging ability. The measurement position in the axial direction of the photosensitive member was the central position.
“Sensitivity”: After adjusting the main charger current so that the dark portion potential at the developing device position becomes a constant value, a predetermined white paper having a reflection density of 0.01 or less is used for the original, and the bright portion at the developing device position. Evaluation is performed based on the image exposure light amount when the image exposure light amount is adjusted so that the potential becomes a predetermined value. Therefore, the smaller the image exposure light amount, the better the sensitivity. The measurement position in the axial direction of the photosensitive member was the central position.
“Optical memory”: After adjusting the current value of the main charger so that the dark portion potential at the developing device position becomes a predetermined value, the bright portion potential when the predetermined white paper is used as the original value Adjust the image exposure light quantity. In this state, a Canon ghost test chart (part number: FY9-9040) with a black circle with a reflection density of 1.1 and a diameter of 5 mm is placed on the document table, and a Canon halftone chart is placed on top of it. In the copied image, the difference between the reflection density of the black circle with a diameter of 5 mm and the reflection density of the halftone portion of the ghost chart recognized on the halftone copy was measured.
“Unevenness of charging ability / sensitivity”... The charging ability and sensitivity were measured at 35 points at lcm intervals in the direction of the photosensitive member axis by the above-described method, and evaluated by the difference between the maximum value and the minimum value.
“Comprehensive image characteristics”: The copy image was comprehensively judged including image flow, image defects caused by spherical protrusions on the drum, and the like.
The evaluation results are shown in Table 2. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was sufficiently suppressed by the present invention.
[0020]
[Example 2]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, in the same manner as in Example 1, a charge injection blocking layer and a photoconductive layer were formed on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm under the conditions shown in Table 1. A photoreceptor comprising a layer and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 450 MHz as in the first embodiment. The total length of the electrodes is 400 mm, and the outer conductor 401 is made of SUS304 having an outer diameter of 40 mm and an inner diameter of 36 mm. The inner conductor 402 has a cylindrical shape with an outer diameter of 10 mm. Further, five slits 403 in the outer conductor axial direction and three in the circumferential direction are arranged in total. The positions of the slits are as shown in FIG. 4- (1), and a, c, e, g, i, k = 25 mm, b = 50 mm, d = 40 mm, f = 30 mm, h = 60 mm, j = 70 mm. The slit width (circumferential direction) was 30 mm.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are “Charging Ability”, “Sensitivity”, “Optical Memory”, “Charging Ability / Sensitivity Unevenness”, and “Comprehensive Image Characteristics”. Was done.
The evaluation results are shown in Table 2. In all items, good results were obtained, and it was confirmed that an a-Si photoconductor having very excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention.
[0021]
(Comparative Example 1)
Except for using a SUS304 rod-shaped electrode having a diameter of 40 mm and a length of 400 mm as the high-frequency electrode, charge injection was performed under the conditions shown in Table 1, using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. A photoreceptor comprising a blocking layer, a photoconductive layer, and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 450 MHz as in the first embodiment.
The produced a-Si photosensitive member was installed in a Canon copier NP-6060 modified for the test used in Example 1, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done.
The evaluation results are shown in Table 2. Compared with Examples 1 and 2, the charging ability and sensitivity unevenness were large, and other characteristics were insufficient as compared with Examples 1 and 2.
[0022]
[Table 1]

[0023]
[Table 2]

[Example 3]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, an electrode having the structure shown in FIG. 4- (2) is used as a high-frequency electrode, and a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm is shown in Table 3. A photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was produced under the conditions. The oscillation frequency of the VHF power supply 312 was 20 MHz. The total length of the electrode is 400 mm, and the outer conductor 401 is made of SUS304 having an outer diameter of 20 mm and an inner diameter of 16 mm. The inner conductor 402 has a cylindrical shape with an outer diameter of 8 mm, and a protruding portion as shown in FIG. The protrusions are 6 mm smaller on each side than the slit shape and protrude 2 mm outward from the outer conductor surface. A total of 15 slits 403 were arranged, 5 in the outer conductor axial direction and 3 in the circumferential direction. The arrangement positions of the slits are as shown in FIG. 4- (2), and a, c, e, g, i, k = 25 mm, b, j = 60 mm, d, h = 50 mm, f = 30 mm. . The slit width (circumferential direction) was 15 mm.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 4. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention.
[0024]
(Comparative Example 2)
Except for using a SUS304 rod-shaped electrode having a diameter of 20 mm and a length of 400 mm as a high-frequency electrode, charge injection was performed under the conditions shown in Table 2 using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. A photoreceptor comprising a blocking layer, a photoconductive layer, and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was 20 MHz as in the third embodiment. The produced a-Si photosensitive member was placed in a Canon copier NP-6060 modified for the test used in Example 2, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 4. Compared with Example 3, the characteristics were insufficient, and a large difference was observed particularly in uneven charging ability and sensitivity.
[0025]
[Table 3]

[0026]
[Table 4]

[Example 4]
The electrode used in Example 2 was modified, and as shown in FIG.²A Teflon material formed at a density of 5 mm was embedded to obtain an electrode for this example. 5B is a cross-sectional view taken along the line BB ′ in FIG. 5A. Reference numeral 501 denotes an outer conductor, 502 denotes an inner conductor, and 503 denotes a slit provided in the outer conductor 501. Is buried by. As described above, the Teflon material is 1 piece / cm.²A gas outlet 506 having a diameter of 1 mm and a diameter of 1 mm is provided. Reference numeral 504 denotes a coaxial portion, and 505 denotes a non-coaxial portion. Such an electrode was installed in the a-Si photoconductor manufacturing apparatus shown in FIG. 3, and the source gas introduction pipe 351 shown in FIG. 3 was removed. Instead, a source gas is introduced between the inner conductor and the outer conductor of the high-frequency electrode 302 having the structure shown in FIG. 5, and the inside of the film forming space is formed from a gas jet (506 in FIG. 5) provided in the Teflon material in the slit portion. Introduced raw material gas.
With such an apparatus configuration, a photoreceptor composed of a charge injection blocking layer, a photoconductive layer, and a surface layer was produced on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm under the conditions shown in Table 5. The oscillation frequency of the VHF power supply 312 was 105 MHz. The total length of the electrodes is 400 mm, the outer conductor 501 is made of SUS304 having an outer diameter of 40 mm and an inner diameter of 36 mm, and the inner conductor 502 is a cylindrical shape having an outer diameter of 10 mm. In addition, five slits 503 are arranged in the outer conductor axial direction and three in the circumferential direction, for a total of fifteen. The arrangement positions of the slits and the dimensions of each slit were the same as those in Example 2. The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 6. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention. Further, in this example, the high-frequency electrode and the raw material gas introduction pipe were used in combination, so that spherical projections on the produced photoreceptor were reduced, and an extremely good electrophotographic image with very few image defects was obtained.
[0027]
(Comparative Example 3)
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, a SUS304 rod electrode having a diameter of 401 mm and a length of 400 mm was used as the high-frequency electrode under the conditions shown in Table 5 in the same manner as in Example 4; A photoreceptor comprising a conductive layer and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 105 MHz as in the fourth embodiment.
The produced a-Si photosensitive member was placed in a Canon copier NP-6060 modified for the test used in Example 4, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Went.
The evaluation results are shown in Table 6. Compared to Example 4, the characteristics were insufficient, and a large difference was observed particularly in charging ability / sensitivity unevenness and image defects due to spherical protrusions on the photoreceptor.
[0028]
[Table 5]

[0029]
[Table 6]

[Example 5]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, the electrode having the structure shown in FIG. 6 is used as the high-frequency electrode, and charge transport is performed on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm under the conditions shown in Table 7. A photoreceptor comprising a layer, a charge generation layer, and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was 200 MHz. The total length of the electrode is 400 mm, and the outer conductor 602 is made of SUS304 having an outer diameter of 20 mm and an inner diameter of 16 mm. The inner conductor 603 has a cylindrical shape with an outer diameter of 8 mm. The high-frequency power radiation portion 601 is made of SUS304 and has a cylindrical shape with an outer diameter of 30 mm and a thickness of 1 mm. A columnar high-frequency power dividing path 604 having a diameter of 2 mm is connected from the inner conductor 603 to the high-frequency power radiation portion 601 through a hole having a diameter of 6 mm provided in the outer conductor 602. Three high-frequency power dividing paths 604 are provided at 120-degree intervals in the circumferential direction at each point. Five high-frequency power dividing paths 604 are arranged in the direction of the outer conductor axis, and dimensions of each part are a, k = 15 mm, b, d, f, h, j = 50 mm, c, e, g, i = 30 mm. is there.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 8. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was sufficiently suppressed by the present invention.
[0030]
[Example 6]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, a charge transport layer and a charge generation layer were formed on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm in the same manner as in Example 5 under the conditions shown in Table 7. A photoreceptor composed of a surface layer was prepared. The oscillation frequency of the VHF power supply 312 was 200 MHz. The total length of the electrode is 400 mm, and the outer conductor 602 is made of SUS304 having an outer diameter of 20 mm and an inner diameter of 16 mm. The inner conductor 603 has a cylindrical shape with an outer diameter of 8 mm. The high-frequency power radiation portion 601 is made of SUS304 and has a cylindrical shape with an outer diameter of 30 mm and a thickness of 1 mm. A columnar high-frequency power dividing path 604 having a diameter of 2 mm is connected from the inner conductor 603 to the high-frequency power radiation portion 601 through a hole having a diameter of 6 mm provided in the outer conductor 602. Three high-frequency power dividing paths 604 are provided at 120-degree intervals in the circumferential direction at each point. Five high-frequency power dividing paths 604 are arranged in the direction of the outer conductor axis, and dimensions of each part are a, c, e, g, i, k = 25 mm, b = 50 mm, d = 40 mm, f = 30 mm, h = 60 mm, j = 70 mm. The slit width (circumferential direction) was 30 mm.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 8. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention.
[0031]
(Comparative Example 4)
Except for using a SUS304 rod-shaped electrode having a diameter of 20 mm and a length of 400 mm as the high-frequency electrode, charge transport was performed under the conditions shown in Table 7 using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. A photoreceptor comprising a layer, a charge generation layer, and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 200 MHz as in Examples 5 and 6.
The produced a-Si photosensitive member was placed in a Canon copier NP-6060 modified for the test used in Examples 5 and 6, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 8. Compared with Examples 5 and 6, the charging ability and sensitivity unevenness were large, and other characteristics were insufficient as compared with Examples 5 and 6.
[0032]
[Table 7]

[0033]
[Table 8]

[Example 7]
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, the electrode having the structure shown in FIG. 6 was used as the high-frequency electrode in the same manner as in Example 6, and on a cylindrical aluminum cylinder 108 mm in diameter and 358 mm in length, A photoreceptor comprising a charge injection blocking layer, a photoconductive layer, and a surface layer was produced under the conditions shown in FIG. The oscillation frequency of the VHF power supply 312 was 450 MHz. The total length of the electrode is 400 mm, and the outer conductor 602 is made of SUS304 having an outer diameter of 30 mm and an inner diameter of 26 mm. The inner conductor 603 has a cylindrical shape with an outer diameter of 15 mm. The high-frequency power radiation unit 601 is made of SUS304 and has a cylindrical shape with an outer diameter of 40 mm and a thickness of 1 mm. A columnar high-frequency power dividing path 604 having a diameter of 2 mm is connected from the inner conductor 603 to the high-frequency power radiation portion 601 through a hole having a diameter of 8 mm provided in the outer conductor 602. Three high-frequency power dividing paths 604 are provided at 120-degree intervals in the circumferential direction at each point. Five high-frequency power dividing paths 604 are arranged in the direction of the outer conductor axis, and dimensions of each part are a, c, e, g, i, k = 25 mm, b = 50 mm, d = 40 mm, f = 30 mm, h = 60 mm, j = 70 mm. The slit width (circumferential direction) was 30 mm.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. Table 10 shows the evaluation results. In all items, good results were obtained, and it was confirmed that an a-Si photoconductor having very excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention.
[0034]
(Comparative Example 5)
Except for using a SUS304 rod-shaped electrode having a diameter of 30 mm and a length of 400 mm as the high-frequency electrode, charge injection was performed under the conditions shown in Table 9 using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. A photoreceptor comprising a blocking layer, a photoconductive layer, and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 450 MHz as in the seventh embodiment.
The produced a-Si photosensitive member was set in a Canon copier NP-6060 modified for the test used in Example 7, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. Table 10 shows the evaluation results. Compared with Example 7, the characteristics were insufficient, and in particular, a large difference was observed in chargeability and sensitivity unevenness.
[0035]
[Table 9]

[0036]
[Table 10]

[Example 8]
The electrode used in Example 6 was modified so that the source gas can flow between the outer conductor 602 and the inner conductor 603, and the electrode was installed in the a-Si photoconductor manufacturing apparatus shown in FIG. The source gas introduction pipe 351 shown in FIG. The source gas passes between the outer conductor 602 and the inner conductor 603, passes through the high-frequency power dividing path hole provided in the outer conductor 602, passes between the outer conductor 602 and the high-frequency power radiating unit 601, and then is formed into a film formation space. Supplied.
With such an apparatus configuration, a photoreceptor composed of a charge injection blocking layer, a photoconductive layer, and a surface layer was produced on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm under the conditions shown in Table 11. The oscillation frequency of the VHF power supply 312 was 20 MHz. The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 12. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention. Further, in this example, the high-frequency electrode and the raw material gas introduction pipe were used in combination, so that spherical projections on the produced photoreceptor were reduced, and an extremely good electrophotographic image with very few image defects was obtained.
[0037]
(Comparative Example 6)
Using the electrophotographic photoreceptor manufacturing apparatus shown in FIG. 3, a SUS304 rod-shaped electrode having a diameter of 20 mm and a length of 400 mm was used as the high-frequency electrode under the conditions shown in Table 11 in the same manner as in Example 4; A photoreceptor comprising a conductive layer and a surface layer was produced. The oscillation frequency of the VHF power supply 312 was set to 20 MHz as in the eighth embodiment.
The produced a-Si photosensitive member was placed in a Canon copier NP-6060 modified for the test used in Example 8, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 12. Compared with Example 8, the characteristics were insufficient, and a large difference was observed particularly in charging ability / sensitivity unevenness and image defects caused by spherical protrusions on the photoreceptor.
[0038]
[Table 11]

[0039]
[Table 12]

[Example 9]
The electrode used in Example 6 was modified to allow He gas to flow between the outer conductor 602 and the inner conductor 603, and the electrode was installed in the a-Si photoconductor manufacturing apparatus shown in FIG. The He gas passes between the outer conductor 602 and the inner conductor 603, passes through the high-frequency power dividing path hole provided in the outer conductor 602, passes between the outer conductor 602 and the high-frequency power radiating unit 601, and then forms a film formation space. Supplied to. The flow rate of He gas was 1000 sccm. On the other hand, the source gas is supplied from the source gas introduction pipe 351 to the film formation space.
With such an apparatus configuration, a photoreceptor composed of a charge injection blocking layer, a photoconductive layer, and a surface layer was produced on a cylindrical aluminum cylinder having a diameter of 108 mm and a length of 358 mm under the conditions shown in Table 13. The oscillation frequency of the VHF power supply 312 was 300 MHz.
The a-Si photosensitive member produced under such conditions was placed in a Canon copier NP-6060 modified for this test, and the characteristics of the photosensitive member were evaluated. The evaluation items are five items of “charging ability”, “sensitivity”, “optical memory”, “charging ability / sensitivity unevenness”, and “total image characteristics”. Was done. The evaluation results are shown in Table 14. Good results were obtained in any of the items, and it was confirmed that an a-Si photoconductor having excellent characteristics was produced in a state where the characteristic unevenness was suppressed extremely uniformly by the present invention.
[0040]
[Table 13]

[0041]
[Table 14]

[0042]
【The invention's effect】
As described above, the present invention can uniformly supply high-frequency power into the film formation space by adjusting the supply ratio of the high-frequency power, and can increase the size of the apparatus by achieving uniformization of a large area plasma. Therefore, it is possible to manufacture a deposited film having a uniform film quality and a uniform film thickness over a large area, regardless of the film formation conditions, without increasing the cost and destabilizing the plasma.
In particular, when an a-Si photoconductor is manufactured using VHF power of 20 to 450 MHz, the electrical characteristics such as charging ability and sensitivity and the image characteristics such as optical memory, image flow, and image defect are good, and the charging ability. It is possible to produce a good a-Si-based photoreceptor in which unevenness in sensitivity and sensitivity are extremely reduced.
Further, when the high-frequency power supply electrode according to the present invention is also used as the raw material gas introduction pipe, it is possible to more effectively suppress image defects.
[Brief description of the drawings]
FIG. 1 is a view showing an example of a high-frequency power supply electrode that can be used in an a-Si photoconductor manufacturing apparatus of the present invention.
FIG. 2 is a view showing an example of a high-frequency power supply electrode that can be used in the a-Si photoconductor manufacturing apparatus of the present invention.
FIG. 3 is a schematic view showing an example of an a-Si photoconductor manufacturing apparatus that can be used in the present invention.
FIGS. 4A and 4B are diagrams showing an example of a high-frequency power supply electrode used in Examples 1 and 2 of the present invention, and FIG. 4B is an example of a high-frequency power supply electrode used in Example 3 of the present invention.
FIG. 5 is a diagram showing an example of a high-frequency power supply electrode used in Example 4 of the present invention.
FIG. 6 is a view showing an example of a high-frequency power supply electrode used in Examples 5 to 9 of the present invention.
FIG. 7 is a schematic configuration diagram showing an example of an electrophotographic light-receiving member manufacturing apparatus by an RF plasma CVD method using a conventional RF band frequency.
FIG. 8 is a schematic configuration diagram showing an example of an electrophotographic light-receiving member manufacturing apparatus by a MW plasma CVD method using a conventional MW band frequency.
FIG. 9 is a diagram showing an example of a layer structure of an a-Si type photoreceptor.
[Explanation of symbols]
101, 401, 501, ... External conductor
102, 402, 502... Internal conductor
103, 403, 503 ... slit
104, 504 ... Coaxial part
105, 505 ... Non-coaxial part
506 ... Gas outlet
201, 601 ... High-frequency power radiation section
202, 602 ... External conductor
203, 603 ..... Internal conductor
204, 604 ... High-frequency power divider
301 ... Reaction vessel
302 ... VHF electrode
304 ... Exhaust pipe
305 ... Cylindrical substrate
306 ..... deposition space
307 ..... heating element
308 ・ ・ ・ ・ ・ Rotary axis
309 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Motor
310 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Reduction gear
311 ... High-frequency matching box
312: High frequency power supply
351 ... Raw material gas introduction pipe
7100 ...... Deposition equipment
7111: Reaction vessel
7112 ... Cylindrical substrate
7113 ... Heater for heating the support
7114 ... Raw material gas introduction pipe
7115 ... Matching box
7116 ... Raw material gas piping
7117 ... Reaction vessel leak valve
7118 ... Main exhaust valve
7119 ... Vacuum gauge
7200 ... Raw material gas supply device
7211-7216 ... Mass flow controller
7221-7226 ... Raw material gas cylinder
7231-7236 ... Raw material gas cylinder valve
7241-7246 ... Gas inlet valve
7251-7256 ... Gas outflow valve
7261-7266 ... Pressure regulator
801 ... Reaction vessel
802 ... Dielectric window
803 ... waveguide
804 ... Exhaust pipe
805 ... Cylindrical base
806 ・ ・ ・ ・ ・ ・ ・ ・ ・ Deposition questions
807 ..... heating element
808 ..... axis of rotation
809 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Motor
810 ..... Reduction gear
851 ... Raw material gas introduction pipe
900... Electrophotographic photoreceptor
901 ... Support
902 ... Photoconductive layer
903 ... Surface layer
904... Charge injection blocking layer
905... Charge generation layer
906 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Charge transport layer

Claims (7)

In the apparatus for producing a deposited film by a plasma CVD method, which has means for introducing at least a source gas and a high-frequency power into a reaction vessel having a film formation space, and forms a deposited film on a substrate in the reaction vessel, the high-frequency power In order to adjust the high-frequency power supply ratio, the means for introducing the high-frequency power is configured to adjust the supply ratio of the high-frequency power to adjust the supply ratio of the high-frequency power. An apparatus for producing a deposited film , wherein a slit is formed in an outer conductor of a coaxial structure transmission line composed of an outer conductor and an inner conductor of the high-frequency power supply electrode . 2. The deposited film manufacturing apparatus according to claim 1 , wherein the inner conductor partially protrudes on the same surface of the outer conductor or outside thereof through a slit provided in the outer conductor. The supply ratio of the high-frequency power includes the area of the high-frequency power radiating portion that is electrically connected by a high-frequency power dividing path that is arranged on the outer periphery of the outer conductor and branches from the inner conductor, and the distance between the high-frequency power radiating portion and the outer conductor 2. The apparatus for producing a deposited film according to claim 1, wherein adjustment is made according to a distance between the high-frequency power dividing path branched from the inner conductor and the outer conductor. The high frequency power supply electrodes has any one of claims 1 to 3, characterized in that to supply the film-forming space than by introducing a raw material gas electrode surface between its outer conductor and the inner conductor The deposited film manufacturing apparatus according to Item. Deposited film manufacturing apparatus according to any one of claims 1 to 4, characterized in that the film-forming space is surrounded by a plurality of cylindrical substrates. The frequency of the said high frequency electric power is 20 MHz or more and 450 MHz or less, The manufacturing apparatus of the deposited film of any one of Claims 1-5 characterized by the above-mentioned. In the method for producing a deposited film by a plasma CVD method, which has means for introducing at least a raw material gas and a high frequency power into a reaction vessel having a film formation space, and forms a deposited film on a substrate in the reaction vessel, the high frequency power Transmission of VHF power having a frequency of 20 MHz to 450 MHz into the film formation space from the high frequency power supply electrode of the means for introducing the power into the film forming space, and the ratio of the coaxial transmission comprising the outer conductor and the inner conductor of the high frequency power supply electrode A method for producing a deposited film, characterized in that the deposited film is produced by uniformly supplying the film into the deposition space by adjusting with a slit formed in an external conductor of the path .

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